CN110034292B - Three-dimensional ordered porous polypyrrole/zinc oxide lithium ion battery negative electrode material and preparation method thereof - Google Patents
Three-dimensional ordered porous polypyrrole/zinc oxide lithium ion battery negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a three-dimensional ordered porous polypyrrole/zinc oxide lithium ion battery cathode material. The electrode material comprises a polypyrrole material and loaded ZnO nanoparticles, wherein the loaded mass percentage of ZnO is 20-60%; wherein, the carrier polypyrrole material has a three-dimensional ordered porous structure, namely contains single, ordered arranged and interconnected macropores: the pore diameter is 300-500 nm. The invention uses sol-gel method to make ZnO nano-particles grow in situ on the porous pore wall of PPy. The excellent conductivity of PPy can provide a good conductive path for zinc oxide, and the mutually connected porous pore channels can accelerate the transmission of lithium ions and electrolyte in the electrode material, so that the cycle performance of the lithium ion battery is improved.
Description
The technical field is as follows:
the technical scheme of the invention relates to preparation of a lithium ion negative electrode material, in particular to a preparation method of a zinc oxide/PPy negative electrode material for a lithium ion battery.
Background art:
lithium ion batteries have the advantages of high working voltage, long cycle life, good safety performance, no public hazard, no memory effect and the likeHave been widely used in portable electronic devices such as mobile phones, cameras, notebook computers, and the like. In recent years, with the increasing and development of hybrid electric vehicles and electric vehicles, the development of lithium ion batteries with high energy, high power density and good cycle performance is an urgent need for the development of the present society. Graphite materials are commonly used as the negative electrode materials of the current commercial lithium ion batteries, but due to the low theoretical specific capacity (372mAh g)-1) The application of graphite-based negative electrode materials in high-energy density chemical power sources is limited, so that the development of novel high-performance negative electrode materials is an urgent task. In recent years, transition metal oxides (MOx, M: Fe, Co, Ni, Zn, etc.) have attracted much attention due to their high theoretical specific capacities and low production costs, and are expected to become negative electrode materials for next-generation lithium ion batteries. Among them, ZnO has a high theoretical specific capacity (978mAh g)-1) Low production cost, environmental protection and the like. However, the lithium ion battery cathode material has a severe volume expansion effect and agglomeration phenomenon in the electrochemical reaction process, and the cycle and rate performance of the electrode material are seriously affected. To overcome these problems, various nanostructured ZnO materials (e.g., nanotubes, hollow nanospheres, single crystal nanorods, etc.) have been developed to improve the active material utilization. Although the nano ZnO material can reduce the diffusion length of lithium ions and adapt to the insertion/extraction mechanical strain of lithium ions in the material, the nano ZnO material still has the disadvantages of poor thermodynamic stability, easy aggregation and the like due to high specific surface area and surface energy. Therefore, it is very necessary to compound ZnO nanoparticles with a protecting group material to further improve the performance of the electrode material. Porous carbon materials, graphene, carbon nanotubes, and the like have been widely used as protective groups because of their large specific surface area and excellent conductivity, but these carbon materials have problems such as structural collapse during the reaction process and poor stability due to the falling off of active materials.
Polypyrrole (PPy) is a typical soft conductive polymer, has the advantages of good conductivity, adjustable conductivity, strong corrosion resistance, good air stability, environmental friendliness, nontoxicity, good biocompatibility, light specific gravity, simple preparation method, low production cost and the like, and can enhance the conductivity and structural stability of the electrode material of the lithium ion battery when serving as a coating or a substrate of the lithium ion battery. Research shows that PPy has good mechanical flexibility and chemical stability in an electrochemical process. The ZnO nano-particles and the PPy are compounded to be used as the lithium ion battery cathode material, so that the conductivity of ZnO can be obviously improved. However, the small specific surface area of PPy limits the high dispersion of ZnO nanoparticles and the diffusion of the electrolyte during the reaction. The three-dimensional ordered porous PPy has the advantages of adjustable aperture, high specific surface area and the like, and is beneficial to improving the dispersibility of ZnO nanoparticles and reducing the particle size of ZnO particles. In the reaction process, the agglomeration of the nano material can be effectively limited, so that the cycle performance of the lithium ion battery is improved.
The invention content is as follows:
the invention aims to provide a three-dimensional ordered porous polypyrrole/zinc oxide lithium ion battery negative electrode material and a preparation method thereof, aiming at the defects in the prior art. The problems of poor conductivity, easy shedding and the like existing when single zinc oxide is used as a negative electrode are solved by compounding ZnO and porous PPy. The technical scheme adopted by the invention is to synthesize a three-dimensional ordered porous polypyrrole material by using a silicon dioxide submicron sphere array as a template. ZnO nanoparticles are uniformly loaded on the porous pore walls of the PPy by using a sol-gel method. The excellent conductivity of PPy can provide a good conductive path for zinc oxide, and the mutually connected porous pore channels can accelerate the transmission of lithium ions and electrolyte in the electrode material, so that the cycle performance of the lithium ion battery is improved.
The technical scheme adopted by the invention is as follows:
the three-dimensional ordered porous polypyrrole/zinc oxide lithium ion battery cathode material is characterized in that the composition of the electrode material comprises a polypyrrole material and loaded ZnO nanoparticles, wherein the loaded mass percentage of ZnO is 20-60%; wherein, the carrier polypyrrole material has a three-dimensional ordered porous structure, namely contains single, ordered arranged and interconnected macropores: the pore diameter is 300-500 nm.
The particle size of the ZnO nanoparticles is 3.0-10.0 nm.
The preparation method of the three-dimensional ordered porous polypyrrole/zinc oxide lithium ion battery negative electrode material comprises the following steps:
(1) preparing a silica microsphere sol: dispersing the silicon dioxide microspheres into an aqueous solution to obtain monodisperse silicon dioxide microsphere sol with the mass fraction of 10% -30%;
(2) placing the monodisperse silicon dioxide microsphere sol into a container, sealing, and standing for 10-20 days; unsealing, taking out supernatant liquor, and continuously standing for 5-10 days until the solution is completely volatilized to obtain a dry silicon dioxide template;
(3) three-dimensional ordered porous polypyrrole material: dissolving pyrrole and sodium acetate in deionized water, adding the silicon dioxide template prepared in the previous step, and finally adding 0.2-0.4M FeCl3Reacting the aqueous solution in an ice-water bath for 10-15 h, taking the silicon dioxide template deposited with the polypyrrole out of the solution after the reaction is finished, and cleaning the surface of the template by using deionized water to remove the polypyrrole; soaking the compound of polypyrrole and silicon dioxide in an HF solution for 12-24h, and cleaning to obtain a three-dimensional ordered porous polypyrrole material;
wherein, 0.1 to 0.3g of pyrrole and 0.1 to 0.3g of sodium acetate are added into every 5 to 10mL of deionized water, and 0.5 to 2g of silicon dioxide template prepared in the previous step and 10mL of FeCl are added3An aqueous solution;
(4) preparing three-dimensional ordered porous polypyrrole loaded ZnO nanoparticles: ultrasonically dispersing 0.3-0.5g of the obtained three-dimensional ordered porous polypyrrole material into 15-30mL of methanol; dissolving 0.2-1g of zinc acetate in 15-30mL of methanol, mixing the two solutions, and continuously stirring at 40-70 ℃ for 1-2h to obtain a solution A; dissolving 0.15-0.5g of potassium hydroxide in 15mL of methanol, and heating to 40-70 ℃ to obtain a solution B; then, adding the solution B into the solution A in a dropwise or spraying mode and continuously stirring for 2-4 hours; finally, centrifugally cleaning and drying the precipitate to obtain three-dimensional ordered porous polypyrrole-loaded ZnO nanoparticles;
the sphere diameter of the microspheres in the monodisperse silicon dioxide microsphere sol is 300-500 nm.
The monodisperse silicon dioxide microspheres in the step (1) are utilized
The preparation method is adopted.
And (4) oxidizing zinc acetate by using excessive potassium hydroxide solution to obtain ZnO nanoparticles.
The dropping time in the step (4) is preferably 15-30 min.
The mass percentage concentration of the HF solution in the step (3) is 5-20%.
The preparation method of the zinc oxide/PPy composite material used for the cathode material of the lithium ion battery is that the raw materials are all obtained commercially, and the equipment and the process are all well known by the technical personnel in the technical field
The invention has the substantive characteristics that:
the inventor works earlier to prepare the three-dimensional ordered porous carbon material loaded zinc oxide nano-particles, but the carbon material has the defects of easy electrochemical corrosion, structural collapse and the like in the reaction. According to the invention, zinc oxide nanoparticles and three-dimensional ordered porous polypyrrole with good conductivity are combined to prepare the negative electrode material of the lithium ion battery for the first time. Oxide-based negative electrode materials generally use carbon materials as carriers, but carbon materials are easily electrochemically corroded in the reaction process, so that the loaded oxide materials fall off, and the capacity is attenuated. The polypyrrole material has good conductivity and a stable structure, and is used as a carrier of the zinc oxide nanoparticles, so that the stability of the electrode material can be improved. However, the polypyrrole material has a small specific surface area and cannot well anchor the zinc oxide nanoparticles, and the porous polypyrrole material is invented to load the zinc oxide nanoparticles aiming at the defect of polypyrrole. In the preparation method, small nano zinc oxide particles are loaded on the walls of the large pores of the three-dimensional ordered porous polypyrrole by a sol-gel method with an excessive oxidizing agent KOH.
The invention has the beneficial effects that:
1. the invention utilizes the silicon dioxide hard template to prepare the conductive high polymer polypyrrole with large specific surface area, developed pore structure and specific morphology. The pore size of the PPy can be controlled by adjusting the particle size of the silica microspheres by using a hard template method.
2. The composite material of zinc oxide/PPy prepared by the sol-gel method can ensure that nano zinc oxide particles are uniformly distributed on the pore walls of the PPy macropores, and the nano zinc oxide particles are small (when the content of ZnO is 20 wt%, the particle size of ZnO is less than 5nm) and uniform in size. The ZnO particles are reduced, the specific surface area is increased, and more reactive sites can be provided. The synthesis process has the advantages of simple preparation method, low cost, environmental friendliness and the like.
The polypyrrole and the nano zinc oxide particles are compounded to be used as the lithium ion battery cathode material, so that the problems of volume expansion effect, agglomeration phenomenon and the like existing when single zinc oxide is used as the lithium ion battery cathode material can be solved, and the cycle performance of the electrode material is enhanced (at 1A g)-1At a current density of 899mAh g after 200 cycles-1Capacity of (d).
Description of the drawings:
FIG. 1 is a TEM photograph of the ZnO/PPy (ZnO content: 20 wt%) obtained in example 1.
FIG. 2 is an X-ray diffraction chart of ZnO/PPy (ZnO content: 20% by weight) obtained in example 1.
FIG. 3 is a TEM photograph of the ZnO/PPy (ZnO content: 60 wt%) obtained in example 5.
FIG. 4 is a specific discharge capacity curve of the PPy-loaded zinc oxide composite material obtained in example 5 as a negative electrode material of a lithium ion battery.
Detailed Description
The process of the present invention is further illustrated below with reference to examples. These examples further describe and illustrate embodiments within the scope of the present invention. The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention.
The silica microsphere sol according to the present invention is a known substance, and its preparation can be described in
W,et al.Controlled growth of monodisperse silica spheres in the micron size range.Journal of Colloid&Interface Science,1968,26(1):62-69)。
Example 1
The preparation method of the three-dimensional ordered porous polypyrrole-loaded ZnO nanoparticles comprises the following steps:
(1) 9.0g of deionized water, 30.8mL of ammonia water and 160mL of absolute ethyl alcohol are mixed uniformly under magnetic stirring for later use.
(2) 200mL of ethanol solution containing 10.5g of tetraethyl orthosilicate (TEOS) is prepared and rapidly added into the solution prepared in the step (1). The reaction was magnetically stirred at 25 ℃ for 12 hours to give a white emulsion.
(3) And (3) centrifuging the white emulsion obtained in the step (2) to obtain silica microspheres (the sphere diameter is 300nm), and ultrasonically dispersing the silica spheres into deionized water to prepare silica sphere sol, wherein the mass of the silica microspheres is 10% of the mass of the sol.
(4) And (4) placing 300mL of the monodisperse silicon dioxide microsphere sol obtained in the step (3) into a 500mL wide-mouth bottle, sealing the wide-mouth bottle with a preservative film, and standing for 20 days. The silica microspheres self-assemble into a three-dimensional ordered silica microsphere array under the action of gravity. And taking down the preservative film, taking out the supernatant, and continuously standing for 10 days until the solution is completely volatilized to obtain the dried silicon dioxide template.
(5) Adding 0.3g of pyrrole and 0.3g of sodium acetate into 10mL of water, then adding 1g of the silica template prepared in the step (4), and finally adding 0.2mol L of-1FeCl of310mL of aqueous solution is used as an oxidant and reacted in an ice-water bath for 12 h. And taking the silicon dioxide template deposited with the polypyrrole after the reaction out of the solution, and washing with deionized water to obtain the polypyrrole-silicon dioxide composite.
(6) And (3) soaking the polypyrrole and silicon dioxide composite obtained in the step (5) in 5 wt% HF solution for 24h to remove a silicon dioxide template, and then washing with deionized water for three times to obtain the three-dimensional ordered porous polypyrrole material.
(7) Ultrasonically dispersing 0.4g of the three-dimensional ordered porous polypyrrole material obtained in the step (6) in 30mL of methanol; 0.27g of zinc acetate was dissolved in 30mL of methanol, the two solutions were mixed and stirred at 60 ℃ for 1 hour to give solution A. 0.15g of potassium hydroxide solution was dissolved in 15mL of methanol and warmed to 60 ℃ to obtain solution B. Thereafter, solution B was added dropwise (1-2 drops per second) to solution A with continuous stirring for 2-4 hours. And finally, centrifugally cleaning and drying the precipitate to obtain a ZnO/PPy (ZnO content is 20 wt%) material.
FIG. 1 shows a Transmission Electron Microscope (TEM) image of the ZnO/PPy material prepared in the example, and it can be seen that polypyrrole has a three-dimensional ordered porous structure and a uniform large pore diameter of about 300 nm. The ZnO nanoparticles are present in a uniformly dispersed state. FIG. 2 is an X-ray diffraction (XRD) pattern of the ZnO/PPy material prepared in the present example. Characteristic peaks of amorphous PPy appeared at 20 to 30 °, and the rest of diffraction peaks at diffraction angles of 31.7 °,34.4 °,36.2 °,47.5 °,56.5 °,62.8 ° and 67.9 ° corresponded to characteristic peaks of ZnO wurtzite (JCPDS card, No.36-1451), and zinc oxide showed good crystallinity. The diameter of the nano zinc oxide is calculated to be about 4.8nm by the scherrer equation (D is 0.89 lambda/Bcos theta).
Example 2
The preparation method of ZnO/PPy is the same as that of example 1, except that the amount of TEOS in step (2) is 27.5g, and the prepared silica microspheres have a sphere diameter of 400 nm.
Example 3
The preparation method of ZnO/PPy is the same as that of example 1, except that the amount of TEOS in step (2) is 48.5g, and the sphere diameter of the prepared silica microsphere is 500 nm.
Example 4
The procedure for preparing ZnO/PPy was the same as in example 1, except that zinc acetate and potassium hydroxide were added in amounts of 0.54g and 0.30g in the step (7), to give ZnO/PPy (ZnO content: 40 wt%).
Example 5
The procedure for preparation of ZnO/PPy was the same as in example 1, except that zinc acetate and potassium hydroxide were added in amounts of 0.81g and 0.45g in the step (7), to give ZnO/PPy (ZnO content: 60 wt%).
FIG. 3 shows a TEM image of the ZnO/PPy material prepared in this example, from which it can be seen that ZnO nanoparticles are uniformly dispersed but in a higher amount than in the example.
Fig. 4 is a cycle chart of the ZnO/PPy material prepared in this embodiment as a negative electrode material of a lithium ion battery, in which a ZnO/PPy composite material, a conductive agent ketjen black, and a binder polyvinylidene fluoride are mixed in a ratio of 8:1:1, ground, and added with an N-methylpyrrolidone solution to be uniformly dispersed, and the mixture is coated on a copper foil and placed in an oven for drying, and then the copper foil with the ZnO/PPy active material is cut into a circular pole piece with a diameter of 14mm for later use. The cell was assembled in a glove box filled with argon using a CR2032 type button cell case, and the prepared electrode sheet was used as the negative electrode, the lithium sheet as the positive electrode, the polypropylene film as the separator, and a 1M lithium hexafluorophosphate-containing mixed solution of dimethyl carbonate/diethyl carbonate/ethylene carbonate (volume ratio of three: 1:1) as the electrolyte. After the assembly is finished, constant-current charging and discharging test is carried out on a Xinwei battery tester, the voltage range is 0.01-3V, and the ZnO/PPy negative electrode material shows good circulation stability and high specific discharge capacity which is 1A g-1Has 899mAh g after 100 times of lower circulation-1The capacity of (a) shows good electrochemical performance.
Example 6
The preparation method of ZnO/PPy is the same as example 1 except that in step (7), the solution B is atomized by a spray gun and added to the solution A prepared earlier.
The invention is not the best known technology.
Claims (5)
1. A three-dimensional ordered porous polypyrrole/zinc oxide lithium ion battery cathode material is characterized in that the cathode material comprises a polypyrrole material and loaded ZnO nanoparticles, wherein the loaded mass percentage of ZnO is 20-60%; wherein, the polypyrrole material has a three-dimensional ordered porous structure, namely contains single, ordered arranged and interconnected macropores: the aperture range is 300-500 nm;
the particle size of the ZnO nano-particles is 3.0-10.0 nm; the ZnO nano-particles are loaded on the walls of the large pores of the three-dimensional ordered porous polypyrrole;
the preparation method of the three-dimensional ordered porous polypyrrole/zinc oxide lithium ion battery negative electrode material comprises the following steps:
(1) preparing a silica microsphere sol: dispersing the silicon dioxide microspheres into an aqueous solution to obtain monodisperse silicon dioxide microsphere sol with the mass fraction of 10% -30%;
(2) placing the monodisperse silicon dioxide microsphere sol into a container, sealing, and standing for 10-20 days; unsealing, taking out supernatant liquor, and continuously standing for 5-10 days until the solution is completely volatilized to obtain a dry silicon dioxide template;
(3) three-dimensional ordered porous polypyrrole material: dissolving pyrrole and sodium acetate in deionized water, adding the silicon dioxide template prepared in the previous step, and finally adding 0.2-0.4M FeCl3Reacting the aqueous solution in an ice-water bath for 10-15 h, taking the silicon dioxide template deposited with the polypyrrole out of the solution after the reaction is finished, and cleaning the surface of the template by using deionized water to remove the polypyrrole; soaking the composite of polypyrrole and silicon dioxide in an HF solution for 12-24h, and cleaning to obtain a three-dimensional ordered porous polypyrrole material;
wherein, 0.1 to 0.3g of pyrrole and 0.1 to 0.3g of sodium acetate are added into every 5 to 10mL of deionized water, and 0.5 to 2g of silicon dioxide template prepared in the previous step and 10mL of FeCl are added3An aqueous solution;
(4) preparing three-dimensional ordered porous polypyrrole loaded ZnO nanoparticles: ultrasonically dispersing 0.3-0.5g of the obtained three-dimensional ordered porous polypyrrole material into 15-30mL of methanol; dissolving 0.2-1g of zinc acetate in 15-30mL of methanol, mixing the two solutions, and continuously stirring at 40-70 ℃ for 1-2h to obtain a solution A; dissolving 0.15-0.5g of potassium hydroxide in 15mL of methanol, and heating to 40-70 ℃ to obtain a solution B; then, adding the solution B into the solution A in a dropwise or spraying mode and continuously stirring for 2-4 hours; and finally, centrifugally cleaning and drying the precipitate to obtain the three-dimensional ordered porous polypyrrole-loaded ZnO nanoparticles.
2. The three-dimensional ordered porous polypyrrole/zinc oxide lithium ion battery negative electrode material of claim 1, wherein the sphere diameter of the microspheres in the monodisperse silica microsphere sol in the preparation method is 300-500 nm.
3. The three-dimensional ordered porous polypyrrole/zinc oxide lithium ion battery negative electrode material of claim 1, wherein the silica microspheres in step (1) in the preparation method are prepared by utilizing a ribbon method.
4. The three-dimensional ordered porous polypyrrole/zinc oxide lithium ion battery negative electrode material of claim 1, wherein the dropping time in the step (4) in the preparation method is 15-30 min.
5. The three-dimensional ordered porous polypyrrole/zinc oxide lithium ion battery negative electrode material of claim 1, wherein the mass percentage concentration of the HF solution in the step (3) in the preparation method is 5% -20%.
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